Nickel werner complexes of ring substituted alpha-phenylalkylamines

ABSTRACT

The invention comprises a Werner complex of general formula Ni(SCN)2Xn which is insoluble, or sparingly soluble, in water at room temperature, wherein X is an alpha-arylalkylamine of the formula &lt;FORM:0994027/C2/1&gt; in which R1 is either hydrogen or a primary alkyl group and R2 is a phenyl group carrying two further halogen substituents on the 3- and 4-positions, and n is either 2 or 4. R1 preferably contains 1 to 10, more particularly 1 to 6, carbon atoms. The halogen substituents are conveniently identical and may be chlorine or bromine.  The complexes are made, according to an example, by adding a solution of the arylalkylamine in heptane, or heptane-chloroform mixture, at room temperature to an aqueous solution obtained by dissolving NiCl2.6H2O and KSCN in water, and separating the resulting precipitate by filtration.  Specific examples of amines are a (3,4-dichlorophenyl) ethylamine, a (3,4 - dichlorophenyl) butylamine, a (3,4 - dichlorophenyl) heptylamine, a (3,4 - dibromophenyl) ethylamine.  They may be prepared by reductive amination of the corresponding ketones, for instance by heating with ammonium formate.  Specifications 931,775, 935,099, 937,791 and 945,012 are referred to.ALSO:Clathrates of aromatic hydrocarbons are made using a Werner complex of the general formula Ni(SCN)2Xn, wherein X is an alpha-arylalkylamine of the formula &lt;FORM:0994027/C4-C5/1&gt; in which R1 is either hydrogen or a primary alkyl group and R2 is a phenyl group carrying two halogen substituents on the 3- and 4-positions, and n is 2 or 4.  The clathrates may be made heating a complex Ni(SCN)2X4 with one or more clathratable aromatic hydrocarbons to a temperature at which all the complex is dissociated into Ni(SCN)2X2 and 2X, and then cooling to effect recombination of the components to form the clathrate. Alternatively a complex Ni(SCN)2X2, at least two motor equivalents of amine X and at least one clathratable aromatic hydrocarbon are mixed together to form a clathrate in which the complex is Ni(SCN)2X4.  A mixture of aromatic hydrocarbons containing at least one such clathratable compound can be resolved by forming a clathrate with a complex of the type Ni(SCN)2X4 and the clathratable compound or compounds in the mixture, separating the clathrate from the mixture and dissociating the clathrate, e.g. by heating, treatment with an acid which does not react with the clathrated compounds, steam stripping or elution with an inert solvent.  In examples, isomers of di-isopropylbenzenes, cymenes, ethylisopropylbenzenes, cyclohexyltoluenes, and methylnaphthalenes are separated. Specifications 931,775, 935,099, 937,791 and 945,012 are referred to.

United States Patent 3,177 ,235 NICKEL WERNER COMPLEXES 0F RING SUBSTI- TUTED ALPHA-PHENYLALKYLAMINES Pierre Marie Joseph Ghislaiu de Radzitzky dOstrowick and Jacques Daniel Victor Hanotier, Brussels, Belgium, assignors to Labofina, Brussels, Belgium No Drawing. Filed May 22, 1963, Ser. No. 282,516 Claims priority, application Great Britain, June 4, 1962, 21,532/ 62 6 Claims. (Cl. 260-439) This invention is a continuation-in-part of application \Ser. No. 122,649, filed July 10, 1951, now abandoned,

which is a continuation-in-part of Ser. No. 555,957, filed November 30, 1959, now abandoned, the former application having claimed a priority date of July 19, 1960, for British application Ser. No. 25,171/60, and the latter application having claimed priority dates of December 1, 1958, for British application 38,654 and Octo her 7, 1959, for British application 33,987.

This invention relates to novel, substantially waterinsoluble compositions of the Werner complex type.

The main object of this invention is to provide new chemical compositions of the Werner complex" type which are insoluble in water at room temperature. Such chemical compositions belong to the family described by the general formula MA- X wherein M is a bivalent metal of atomic number greater than 12, A is a monovalent poly-atomic anion, and X is a primary, phenylsubstituted alkylamine of which the alkyl group contains from 1 to 12 carbon atoms, said substituent phenyl group being itself further substituted by at least one polarizable non-hydrocarbon radical, and n is either 2 or 4.

Another object is to prepare Werner complexes with amines which have a negligible ammoniacal odor, and a low vapor pressure.

Still another object is to provide a process for the preparation of the novel Werner complexes.

Other objects and advantages of the present invention will become apparent upon further study of the specification and appended claims.

For the purpose of simplicity the novel compounds of this invention will be described in two sections, the first section being directed to monosubstituted phenylalkylamines, and the second being directed to polysubstituted phenylalkylamines.

MONOSUBSTITUTED PHENYLALKYLAMINES According to the present invention there is provided a compound of the general formula NiA X which is insoluble at room temperature, wherein A is a monovalent triatomic anion which includes one carbon atom only, this carbon atom being directly linked to a nitrogen atom, X is a primary, phenyl-substituted alkylamine of which the alkyl group contains from 1 to 12 carbon atoms, said substituent phenyl group being itself further substituted by one polarizable non-hydrocarbon radical, and n is either 2 or 4.

The triatomic anions A are thiocyanate and selenacyanate or the iso-forms of any of these, the thiocyanate and iso-cyanate being preferred. It is to be understood that no choice is made regarding the form of the anion. By example SCN must be read as a whole and is not restricted specifically to any of the normal or iso form.

The most recent information given in the literature would rather support the idea of an iso configuration wherein Ni is directly linked to the nitrogen atom, but no conclusion is yet possible.

Generally speaking, compounds of the general formula CoA X are comparable to the ones hereabove described, but their sensitivity to oxidation and the resulting instability seriously restrain their industrial uses.

"ice

The present invention particularly comprehends a compound of the general formula Ni(SCN) 2X which is insoluble in water at room temperature, in which X is a primary phenyl-substituted alkylamine of which the alkyl group contains from 1 to 12 carbon atoms, the amine radical being attached to the same carbon atom in the alkyl group as is the phenyl group, that is to say, the amine radical being in the alpha position with respect to the phenyl group and the substituent phenyl group itself has as a substituent a polarizable non-hydrocarbon radical, and n is either 2 or 4. In other words, X is an arylalkylamine of the formulait. wherein R is selected from the group consisting of hydrogen and a primary alkyl group of l-ll carbon atoms, R is a phenyl group being itself substituted with one polarizable radical containing at least one "atom other than carbon and hydrogen, said polarizable radical being chemically inert to said arylalkylamine group.

The polarizable, non-hyd-rocarbonradical is directly linked to the aromatic nucleus in any position with respect to the alkyl group. Suitable polarizable non-hydrocarbon groups are chemically inert to the arylalkylamine radical, i.e., those which do not react with the amine radical either by salt formation or by chemical reaction, do not compete with the coordinating power of the amine group, and do not give rise to any steric hindrance in the complex formation. Preferred polarizable non-hydrocarbon radicals are: halogen, trifluoromethyl-, hydroxy-, nitro-, cyano-, carbamyl-, and sulfamyl. In addition, there are other preferred radicals such as alkoxy and carboalkoxy radicals having from 1 to 5 carbon atoms, and N,N-dialkylamino radicals wherein the alkyl portions contain 1 to 2 carbon atoms.

The most preferred polarizable non-hydrocarbon radicals are the halogens.

Specific examples of the herebefore described class of amines are:

(1) o-Chlorobenzyl'amine O-OICaH4-CH NH1 (2) p-Bromobenzylamine p-BrCaH4 H2NH2 p-Dimethylaminobenzylamine p- (0 Ha) iN C nHr-CHa-NH: a-(p-Fluorophenyl)ethylamine p-FQe 4 i H- s 04- (o-Chlorophenyl) ethylamine 0- Cl-CuHl-(]]H-C H3 a- (p-Chlorophenyl ethylamine p-Cl--CH --(|3HOH;

NH: a-(m-Bromophenyl)ethylamine llkBf-QaHr-(fiH-Cfia 11- (p-Bromophenyl) ethylamine p-Br-CuH4-?HCH:

NH: a-(p-IodophenyDethylamine D"I OBHI?H OH3 oz- (p-Chlorophenyl) propylamine p-OlCoH4-CHCgH oc- (m-Bromophenyl) propylamine m-Bro,Hi-on o,rr, I IHi a- (p Brornophenyl) prop'ylamine p-B r-QaH4-OH-C 1H5 V 11TH: a- (p-Bromophenyl) butylamine p-B rC H C H- 03H, 1 TH, a- (p-Chlorophenyl) amylamine -oi oanr-on-olnn 111E: a- (p-Bromophenyl) amylamine p- BrC H C E 04119 a (pFluorophenyl) is o amylamine p-FCuH4--CHCHgCH (CH3) 1 111B: 7 v oc- (p-Chlorophenyl) isoarnylamine p-ClO H CH-CH -CH(OH is. a- (p-Bromophenyl) isoamylamine p-BrC H CHOH;OH(CH VNH: a- (p -Chlorophenyl hexylamine p- Cl C fiHQ-C H- CsHn V r'm,

u- (p-Bromophenyl) hexylamine p-B 1-CaH4-CH C5H11 7 I'm,

oc- (m-Bromophenyl heptylamine m-BPC5H4OHC H1 oc- (p-Bromophenyl) heptylamine p-B r-Cafh- C H. @HH

a- (p-Bromophenyl) nonylamine p-B 1-0,]14- (EH-08H 11- (p-Chlorophenyl) d odecyl amine oi-oartt-c'n-oum,

a- (p-Methoxyphenyl) ethylamine p'CH OCsH4-CH-CHs I l H3 a- (p -Butoxyphenyl) ethylamine D- 4HuOC H 'CHOH a- (p -Methoxyphenyl) heptylamine D- s oH4 H eHis NH: 11- (m-Nitrophenyl ethylamine -N 2- oH4 HCHj All these amines have little or no ammoniacal odor, difiering markedly in :this respect from heterocyclic nitro-' gen bases, which have a strong and persistant nauseous odor, and the amines of this invention also have a low vapor pressure reducing flammability hazard,

The process of this invention comprises, preparing a compound of the general formulaMA X wherein a salt mits easier formation of the complexes and enables them to be obtained in a purer form. This may be partly explained by the lipophilic character of the complexes, which are protected against hydrolysis bya hydrocarbon phase, there being thus avoided the formation of a gel of a metal hydroxide which would impede crystallization.

Inasmuch as thehydrocarbon'does not enter into the reaction, it is obvious that a wide variety of hydrocarbons can be used. including halogenated derivatives thereof. For-example, there may beused such hydrocarbons as pentane, heptane and cyclohexane.

The complexes MA X are insoluble in water and aliphatic hydrocarbons. They are "sparingly soluble in aromatic hydrocarbons at ordinary temperature, depending on their molecular weight. MA 'X complexes are generally soluble in organic-polar solvents.

These complexes havenumeroususegthey can be dissolved in organic polar solvents, thus permitting the introduction of metals into these solutions, in which they can act as oxidation or polymerization catalysts (e.g. in drying oils). They can also be usedin solution for impregnating catalytic masses. In solid form, they can be used in heterogeneous catalysisor as clathrating agents.

For example, the separation of pure isomers of xylene is an important problem in the petrochemical industry since each isomer may be oxidized to the corresponding phthalic. acid-and phthalic acids enter into the, fabrication of numerous valuable diand polyesters. The quality of such products depends on the purity .ofthe starting isomer of xylene. Clathration by the compounds according to the present invention is a means of resolving mixtures of xylenes. v

In order that the present invention maybe more clear- .ly understood, some preferred examples of the prepara tion of the, new Werner complexes according to the invention will now be described. .However, it is to be understood that these examples are not in any way limita-. tive of the. broad aspects of the inventionas expressed in the'specification and appended claims.

Example l.f-Preparation of Ni scN {oc- (p-bromophenyl) butylamin'eh] A solution of 5.70 gms. (0.025 mole) of u-(p-bromophenyl)butylarnine in 10 ml. of heptane'is slowly added,

while stirring, at room temperature, toabinary mixture comprising 5 ml. of heptane. and an aqueous solution obtained by dissolving 1.32 gms. (0.0056 mole) of NiCl .6H O

and.1.11 gms. (0.0114 mole) of KSCN in 3 of distilled washing removes any remaining salt or unreacted amine. The precipitate is filtered off again and dried in a thin layer under vacuum at room temperature for two hours. The resulting complex is a blue powder conforming to the formula [Ni(SCN) (aminc)4] as shown by the following analysis:

The small differences from the theoretical figures which are observed in the analysis of each constituent are probably due to the presence of a small amount of water which is difi'icult to remove at room temperature.

Example 2.-Preparation of [Ni (SCN 2 {or-(p-methoxyphenyl) ethylamineh] By following exactly the same procedure but using a-(p-methoxyphenyl)ethylamine instead of u-(p-bromophenyl)butylamine, one obtains a blue powdery complex conforming to the formula [Ni(SCN) (aminc)4] as shown by the following analysis:

Example 3.Pareparati0n of [Ni (SCN {u-(pchlor0phenyl)hexylamineh] 7.83 g. (0.0370 mole) of u-(p-chlorophenyl)hexylamine is slowly added, while stirring at the ice-bath temperature, to an aqueous solution of Ni(SCN) obtained by dissolving 2.20 g. (0.0093 mole) of NiC1 -6H O and 1.85 g. (0.0190 mole) of KSCN in 20 ml. of distilled water. During this addition, a blue precipitate is formed which, after further stirring during about minutes, is filtered OE and washed by stirring in ml. of distilled water. Theprecipitate is filtered off again and dried in a thin layer under vacuum at room temperature for two hours. Tht resulting complex is a blue powder conforming to the formula [Ni(SCN) (amine) as shown by the following analysis:

6 Example 4.Preparation of [Ni(SCN) {a-(p-chlorophenyl) dodecylamineh] By following the same procedure but using rz-(pechlorophenyl)dodecylamine instead of u-(p-chlorophenyl) hexylamine, one obtains first a green amorphous precipitate which after further stirring becomes a blue crystalline precipitate which also conforms to formula [Ni(SCN) (amine) as shown by the following analysis:

Constituents Percent Percent theoretical observed Nickel (M) 7 p 4. 3 4.1 Thiocyauate (A) 8. 6 8. 3 Amine (X) 87. 1 88. 2

Molar ratios Theoretical Observed ratios ratios X/M 4. 00 4. 26 AIM 2. 00 2. 04

Example 5.--Preparation of [Ni(SCN) {a-(p-brom0- phenyl)'ethylamine} A solution of 3.70 gms. (0.0185 mole) of a-(p-bromophenyl) ethylarnine in 5 m1. of chloroform is slowly added, while stirring, at room temperature, to a biphasic mixture comprising 5 ml. of chloroform, 10 ml. of heptane and an aqueous solution obtained by dissolving 2.20 gms. (0.0093 mole) of NiCl .6H O and 1.85 gms. (0.019 mole) of KSCN in 10 ml. of distilled water. A crystalline precipitate is readily formed. After stirring for 30 minutes, the resulting precipitate is filtered off and washed twice, first by stirring in a mixture of 10 ml. of heptane and 5 inl. of water, then filtering off and stirring a second time in 10 ml. of chloroform, and filtering olf again. The complex is then dried in a thin layer in a vacuum oven at 110 C. for 5 hours. The resulting complex is a pale green powder conforming to the formula as shown by the following analysis:

It will have been observed from the foregoing examples that the preparation of the complexes containing only two molecules of the amine is identical with the preparation of the complexes containing four such mole. cules except in that half the quantity of amine is used. The two-base complexes are very stable, permitting quick drying at C. even under vacuum.

The use of chloroform provides the two-base complexes in a purer form because they are generally not soluble in this medium, while the four-base complexes are soluble therein, often with decomposition to the corresponding two-base complexes.

One use of the new Werner complexes described, the

[Ni(SCN) {a-(p-bromophenyl)ethylamideh] being prepared and employed to separate a mixture of aromatic hydrocarbons.

Will now be A solution of 0.0400'11'1016 a TABLE I (P- QP Y y p I 1 Molar'ratios in 25 ml. of a mixture of Xylene (in moles percent: :342; rn-= 3O.1; p-=35.7) is slowly added, while stir- 5 X/Ni NCS/Ni ring at ice bath temperature,.to an aqueous solution ob- Y I tained bydissolving 0.0093 mole of NiCl .6H O and fitE28 :8zg g e y a ehl 00190111016 of K SCNin 10 ml. or distilledwater. After ifirfiiobififififiaiiiififiii:Ij 4301 '2: 01 stirring for 30 minutes, the resultmg preclpitatev 1s filtered -gg ggggg gggg lgg gg l z w y y 4. Washed first With p el h W 1fl1 25 m 10 0... Ni(SON)2 a-(p-chlorophenyl)ethylamine 4.13 2.00 of pentane, and then dried 1n air. 7 gms. of this dry preg 4% ll l20 I2-"- clpltate a fil P y Treatlng With 9-.-

a-gp-gromopllienygegiylaminetill; 3.05 2.00 10.. i 2 apromop eny e y amine 2 2.00 2.03 6 N HCl w ereupon 1t separates ii i .orgamc p E 11.- Ni(SGN) a-(p-iodophenynethylaminel4]. 3.91 1.97 and an aqueous P The Grgamc P F186 18 eXtYaCLed 12.- Ni(SCN)z aim-bromophenyl)propyla nine'h] 4.00 1.90 with 5 m1. ofcyclohexane and analyzed by infra-red K M a-(p-b p yD ty ne41 10 14.. N1(SCN)2 a-(p-bromophenyl)butylamme 2].- r 2.13 1. 98 spectrophotometry. It is found that 9.8% of the dry -pmgloropgenygamylamine 4.30 07 1 '1 16 Ni l 2 01- p-c orop eny amy amine 2.-. 2.12. i .96 precipitate consists of Xylene 1somers with a strong en 17" NKSONhIa (p chlomphenyl)hxymmme 41m 415 1.96. nchment of the paraisomer (1n moles percent. 0-=4.8, 18" j iggggg i -Ep.gh1oy0p%eny%hexyl%mi11g ;]j 1,99 1,96 19.- i 2 apromop eny nony amine 4 5.47 V 1.95 m 27.3, p 67.9 the remalnder consisting essentmlly NKSCN 1 1 r0pl1enyl)dodecyla- 4,26 2. 04 of the complex [N1(SCN) (annne) 20 m sk} I i a 21.- Ni(SO )2 a-(p-metho'xyphenyl)ethylamine 4] .4.05 1.97 AS has shown m the Precedmg examples 22.. Ni(SON)2 a-(p-methoxyphenyl)ethylnmine2] 2.01 2. 03 more convenient touse as the source of metal and anion 3 N1:(SON)2 a-(m-nitrophenyl)ethylarninel4]... 4. 02 2. 03 two different salts containing the respective ions. On N1 SCN)2 '(PmmPhenYDethylammeMm- Z03 addition of the primary phenyl-substituted alkylamine I TABLE II Complex [Ni(SON)zXn] 0010: Solubility in methanol [Ni(SON)2(o-chlorobenzylamiuh] Pale blue; ver rsg hu S0 11 0. 2 [Ni(SON) (p-brom0benzylamiue)l] Purple Slightly S0 H e. Ni(SCN)g(p-dimethylaminobenzylamineh Insoluble. Ni(SON)2 ii-(p-fiuorophenybethylamine t1 vVery soluble. Ni(SON) a-(o-chlorophenyl)ethylamine .1 Soluble. Ni(SCN)z a-(p-ehlorophenyl)ethylaminel4] D0.

' Ni(SON) a-(m-bromopheuyl)ethylaminei4]- Very soluble.

a-(rn-bromophenyDethylamine 2]. Soluble. a-(p-bromophenyl)ethylamine 4]-- Do. a-(p-bromophenyl)ethylamine 2].- Do. a-(p-iodophenyl) ethylamine h] lu Slightly,

soluble. a-(pcl1lor0pheny1)propylaminel4] ---do Very soluble a-(m-bromophenyl)propylamiueb1" d I Do.

a-(p-brornophenyl butylamine 4]..-- a-(p-bromophenyl) butylamine 0]. a- (p-chloropheuyl) amylamine i4 a-(p-chlorophenyl)amylamine 2 a-(p-bromophenyl)amylamineh a- (p-brornophenyl) isoamylamine i4 a-(p-bromophenyDisQamyIamlne 2 a-(p-chlorophenyl)hexylamiuei4 a-(p-chlorophenyl)hexylamine uz- (m-bromophenyl) heptylamiue 5 04- (p-bromophenyl) nonylamine l4 01-) p-methoxyphenyl) ethylamine g Very soluble.

0. Soluble. Very soluble.

oluble. Very soluble.

25. 1 N) a 26--- NKSON): 27.-- Ni(SCN)2 28--- [NKSCNlz 29.-- [Ni(S ONM a-(p-methoxyphenyDethylamine 2]-- Palegreen. Soluble. a-(m-nitrophenyl)ethylaminel4] o Slightly soluble. a-(p-nitrophenyl)ethylamine};]--.; Green Soluble. a-(p-chlorophenyl)dodecylamineh] Blue D0.

double decomposition occurs, the sparingly soluble complex being continuously precipitated by displacement of the equilibrium:

NiCl +KSCN+4X(X:amina=ted base) For complexes conforming to the. general formula MAgX (M=metal; A=anion; X=amine), thetheoretical values of the molar ratios A:M and XzM are 2 and 4 respectively when n=4, and 2 and 2 respectively,

The new and unobvious advantagesof the compounds 0t this invention as compared to other Werner complexes are;

Absence of ammoniacal odor Insolubility in water Lowfiammability hazard I Unexpected selectivities in clathration POLYSUBSTITUTED PHENYLALKYLAMINES:

According to this aspect of the. invention, new compleXes .of the Wernerftype: are obtained. from nickel thiocyanate or. nickel selenocyanate', and an aminated base of the alpha-arylalkylamine type, the aryl group of which is a benzene nucleus furthetsubstituted,by12 halogens on the 3 and 4 positions.

According to the invention there is provided a Werner complex of general formula NiA X which 'isginsoluble or sparinglysoluble in water-at room temperature, whereinlA iseither a thiocyanate or selenocyanate anion, X is 'an alpha-arylalkylamine in which the aryl group is a phenyl groupcarryingZ further halogen substituents on the 3 and 4. positions, the" alkyl group being a paraffinic:

9 radical having no side chain on the alpha and beta carbon atoms, n is either 2 or 4. Preferably A is a tbiocyanate anion.

In other words, this aspect of the invention comprises a compound of the general formula Ni(SCN) X which is insoluble or sparingly soluble in water at room temperature, wherein X is an alpha-arylalkylamine having the general formula:

R1 H NH,

in where R is either a hydrogen or a primary alkyl group and R is a 3,4-dihalphenyl group, n is either 2 or 4.

The halogen substituents are conveniently identical and may be for example chlorine, bromine, iodine or fluorine atoms. Preferably both substituents are chlorine atoms.

The number of carbon atoms in the primary alkyl group R may vary within rather broad limits. Nevertheless a probability of getting steric effect impeding the formation of the complex will be met with the higher alkyl groups. Also the solubility and the physical aspect of the complex depend on the length of the chain and the complex will get less and less insoluble in hydrocarbons and more and more waxy as the length of the chain increases.

When used as clathrating agents, the Werner com plexes as defined must remain solid and not dissolve to a large extent in the aromatic compounds to be clathrated. A preferred embodiment of this invention will so comprehend insoluble or slightly soluble complexes in aromatic hydrocarbons at room temperature.

It is thus preferred that there be 1 to about 10, even more preferably 1 to 6 carbon atoms in the alkyl group R Amines, the benzenic ring of which carries one of the two halogen substituents in position 2. or 6, are less suitable for forming complexes wherein n is 4.

Such complexes when they are obtained are also less active clathrating agents.

Specific but not limitative examples of the hereinbefore described class of aminated bases are:

n,, salt, C.

a-(3,4-diehl0ropheny1)ethylamine.

H-C-OH:

a-(3,4,-dlchlorophenyl) butylamlne NHz HC--C3H7 a-(3,4-dichlorophenyl)heptylamina.

H -OsH13 13.1 .1. H01 11 C./mm salt, 0.

a-(3,4-dibromophenyl)ethylamine. 133-5/4 236-7 1. 6057 lTIHr All amines hereinabove described have little or no ammoniacal odor, thus differing markedly from heterocyclic nitrogen bases which exhibit strong and persistant nauseous smelling. In addition, all amines hereinafter described have a very low vapor pressure thus reducing fire risks, which risks are also reduced because of the presence of the two halogen substituents in the amines used.

All amines hereinabove described are also new chemical compounds. They are easily prepared by reductive amination of the corresponding ketones, for instance by heating with ammonium formate (Leuckart reaction).

It is to be noted that no choice is made regarding the form of the anion SCN. The formula SCN must be taken as a whole and not be restricted specifically to any of the normal or iso forms.

Replacement of SCN by SeCN gives also complexes having approximately the same general properties. Nevertheless selenium complexes are much less attractive than SCN because they are not readily available.

The complexes following the invention have numerous uses. They can be dissolved in organic polar solvents, thus permitting the introduction of nickel into these solutions in which they can act as oxidation or polymerization catalysts.

They can also be used in solution for impregnating catalytic masses.

In solid form they can be used as heterogenous catalysts or as clathrating agents.

As clathrating agents, they permit resolution of mixtures'which are difficult to resolve by conventional methods, particularly mixtures of aromatic isomers.

In such uses they show unexpected properties, by example for the treatment of aromatic molecules having at least one bulky group for which they show unexpected selectivities and capacities.

They have also the advantage of being less soluble and less dissociated in aromatic hydrocarbons than the similar complexes not having 2 halogen substituents on the benzene ring. This is particularly noticeable when the length of the alkyl chain R increases.

When compared to complexes of the same general formula but using other types of arylalkylamines, the complexes of this invention exhibit a marked and highly unexpected superiority in clathrating separation processes.

The preparation of the complexes according to the invention will now be described with reference to the following example.

Example 6 .Preparati0n of [Ni (SCN) {oc- (3,4,-dichl0r0phenyl ethylamineh] A solution of 0.0250 mole of a-(3,4-dichlorophenyl) ethylamine in 6 ml. of heptane is slowly added, while stirring at room temperature, to an aqueous solution obtained by dissolving 0.0056 mole of NiCl .6H O and 0.0114 mole of KSCN in 6 ml. of distilled water. After stirring for 30 minutes, the resulting precipitate is then separated by filtration, washed with a mixture of 6 cc. of heptane and 6 cc. of water and dried for 2 hours under vacuum at room temperature.

are prepared in a similar manner.

The two-base complexes are obtainedby using s toichi- 12 Para-diisopropylbehzene is a valuable starting material forthe synthesis of terephtlralic acid. I s

The separation ofpara-diisopropylbenzene out of its isomers by clathration withthe, new Wernercomplexeswill be described withvreference to the following. specific case.

ometric quantities of reactants, re. 2x moles of 3.1111116, at For clathratlng a mixture of dusopr-opylbenzenes (1n moles NiCl .6H O, 2x moles of KCNS, aslight deficitof mole perc n P- y '7 V amine being advisable. Furthermore, the two base com- [Ni(SCN)2{o- (3,4 dich10mpheny1)butylamineh] V plexes are easierto obtam an a pure form when an equal 1 0 0250 1 f 3 4 M h 1 b t 1 quantity of chloroform is added to heptane either for the a H 1 f $9 6 9 Crop E u formation and for the washing of the complexes. Those E d 3 {nix E sqgz y enztenes complexes are then dried for 2 hours under vacuum at S OW y a e W S lmnfga e a empera 0 1001: C I I an aqueous solutionobtained by dJSSOiVlIlg 0.0056 mole For complexes conforming to the general formula f N1C12'6H2O and O'0.1 1.4m01e KSQN'm of Q SCN) X the theoretical Values of the molar ratio tilled Water. Atter stirrmg for 'm1nutesthe resulting 1( 2 1 d 4 h 4 precipitate is then separated by filtration, washed once with SCN 1 1 are respec We y an W en 1S 20 ml. of heptane and once with 20 mlrof pentane, and and 2 when n 15 dried in air. 3 g. of the dry precipitate are decomposed For complexes h descnbed We havefound by func by 10ml. of acetic acid. After decomposition, the tuonal analysis, ratios very close to theoretical values, leavacetic acid is diluted by 20 m1. of distilled Water and the i g 110 (1011b? the Composition of f P 29 clathrated hydrocarbons are extracted by '10; ml. of p- I Soillbllltf/Of 1111? new CPl'l'lPiCXBS [L11 016131131101 has Xylene analyzed by vapopphase chromatography been determined. This solublllty may b mcreased y 7 It is thus found that 14.3% of the solid obtained consist of adding to the methanol some of the corresponding amine. diisopropylbenzene isomers with a strong enrichment of TABLE III I Molar ratios 7 Color 1 Solubility in methanol a X/Nir SON/Ni [Ni(SCN)z a-(sA-dichlorophenyl)ethylaminel4] r nish blue.-. 4. 02 2. e3 Very soluble. [Ni(SON)21a-(3,4-diehlorophenyl)butylamine 41.0- Pale bl 4.00 1. 97 Do. [Ni(SCN)2 a-(3,4-dieh1oropheny1)heptylarnmel4] ue 4.06 2.00 Do. [Ni(SCN)gia-(3,4-diehl0rophenyl)ethylammei2 Pale green 2.03 2. 03 Soluble [Ni(SCN)z a-(3,4-d1bromophenyl)ethylam net2]- .do 1. 94 1. 94 Slightly soluble; Ni s0N) {a-(3,4-dibromophenybethylamaue 4] P blue 4.10 1. 94 oluble.

. Because of their reduced solubility in aromatic hydro carbons the new complexes can be used as clathrating agents in large volumes of said hydrocarbons without loss of said complexes and without any significant contamination of said hydrocarbons.

Some ofthe new complexes are particularly interesting for the separation of para-isomers of bulky aromatic molecules which were either difiicult or impossible to separate by clathration with the previously described complexes.

Para-diisopropylbenzene in admixture with its isomers is found. as a byproduct of the synthesis of cumene.

the para-isomer (in mole percent: o-: 3; m-: 11'; p: 86).

' The remainderconsists essentially of the complex Other resolutions of mixture of aromatic compounds are realized by the same procedure employing the same complex or the other complexes according to the invention; the results of suchclathrations are summarized'together with the preceding results in vTable IV, this shows that not only aromatics carrying bulky alkyl substituents but also some others such as methylnaphthalenes are clathrated with a very good selectivity.

TABLE IV Composition -Clathrated ofthe clathcompounds Aminatcd base of the 4-base complex Comp0s1t1on of the feed rated mixin the (mole percent) ture (mole elathrate percent) (weight percent) w(3,4-diehlorophenyl)ethylamine Oym n s 3 o 5 V m =34.-- 33 20.3

. v V p F 33 a2 a-(3,4-dichlorophenyl)butylamine Ethyhsogopyl benzenes: f

5 t 8? 20.9 a-(3,4-dichlorophenyl)heptylamiria; 3G

12.1 V a-(3,4-dibromophenyl)ethylamine 41 V For additional details regarding clathration techniques, attention is invited to our application directed specifically to clathration processes using the novel complexes of this invention, said application filed simultaneously with the present application.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and without departing from the spirit and scope thereof, can make various changa and modifications of the invention to adapt it to various usages and conditions. Consequently, such changes and modifications are properly, equitably, and intended to be, within the full range of equivalence of the following claims.

What is claimed is:

1. A Werner complex of general formula Ni(CNS) X wherein n is an even number from 1 to 5 and X is a substituted phenylalkylamine having the formula:

Ra H

(ENH2 i l.

s in which R is selected from the group consisting of hydrogen and primary alkyl radicals of 1 to 11 carbon atoms, R is selected from the group consisting of hydrogen and halogen, R is selected from the group consisting of halogen, nitro, alkoxy containing l to 5 carbon atoms, and N,N-dialkylamino wherein the alkyl portions contain 1 to 2 carbon atoms, the radical R being hydrogen when the radical R is other than halogen.

2. A Werner complex following claim 1 in which the radicals R and R are at any of the positions 3 and 4 of the phenyl radical.

3. A Werner complex following claim 1 in which the radicals R and R are at any of the positions 3 and 4 of the phenyl radical and in which R is a primary alkyl radical of 1 to 6 carbon atoms, R is hydrogen and R is selected from the group consisting of halogen, nitro, alkoxy containing 1 to 5 carbon atoms, and N,N-dialkylamino wherein the alkyl portions contain 1 to 5 carbon atoms.

4. A Werner complex following claim 3 in which R is halogen.

5. A Werner complex following claim 1 in which R is a primary alkyl radical of l to 6 carbon atoms, R and R are halogens.

6. A Werner complex following claim 1 in which the amine X is selected from the group consisting of:

o-chlorobenzylamine p-bromobenzylamine p-dimethyl aminobenzylamine alpha- (p fluorophenyl) ethylarnine alphao-chlorophenyl) ethylamine alpha- (m-chlorophenyl) ethylamine alphap-chlorophenyl) ethylamine alpha- (m-bromophenyl ethylamine alpha- (p-bromophenyl) ethylamine alpha- (p-iodophenyl ethylamine alpha- (p-chlorophenyl) propylamine alpha- (m-brornopheny'l) propylamine alpha- (p-bromopheinyl) butylamine alpha- (p-chlorophenyl) amylamine alph a- (p-b romophenyl) amyl amine alph a- (p-bromophenyl isoamylarnine alphap-chlorophenyl) hexy'l amine alpha- (p-fiuorophenyl heptylamine alpha- (m-bromophenyl) heptylamine alpha- (p-brornophenyl) nonylamine alpha- (p-chlorophenyl) dodecylanu'ne alpha- (p-methoxyphenyl) ethylamine valpha- (rn-nitrophenyl ethylamine alpha- 3 ,4-dichlorophenyl) ethylamine alpha- 3 ,4-dibrornophenyl) ethylamine alpha- 3 ,4-dichlorophenyl) butylamine alpha- 3 ,4-dichlorophenyl) heptylamine References Cited by the Examiner UNITED STATES PATENTS 7/57 Schaeifer et a1. 260-439 OTHER REFERENCES TOBIAS E. LEVOW, Primary Examiner. 

1. A WERNER COMPLEX OF GENERAL FORMULA NI(CNS)2 XN WHEREIN N IS AN EVEN NUMBER FROM 1 TO 5 AND X IS A SUBSTITUTED PHENYLALKYLAMINE HAVING THE FORMULA: 